US4072678A - Process for producing caprolactam - Google Patents

Process for producing caprolactam Download PDF

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Publication number
US4072678A
US4072678A US05/698,122 US69812276A US4072678A US 4072678 A US4072678 A US 4072678A US 69812276 A US69812276 A US 69812276A US 4072678 A US4072678 A US 4072678A
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US
United States
Prior art keywords
sulfuric acid
range
combustion
caprolactam
distillate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US05/698,122
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English (en)
Inventor
Fusao Oyama
Sadatomi Murao
Shizuo Okada
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Filing date
Publication date
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Publication of US4072678A publication Critical patent/US4072678A/en
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    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/74—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being orientated, e.g. in parallel (anisotropic fleeces)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
    • C07D201/02—Preparation of lactams
    • C07D201/04—Preparation of lactams from or via oximes by Beckmann rearrangement
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16B—DEVICES FOR FASTENING OR SECURING CONSTRUCTIONAL ELEMENTS OR MACHINE PARTS TOGETHER, e.g. NAILS, BOLTS, CIRCLIPS, CLAMPS, CLIPS OR WEDGES; JOINTS OR JOINTING
    • F16B7/00—Connections of rods or tubes, e.g. of non-circular section, mutually, including resilient connections
    • F16B7/04—Clamping or clipping connections
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23Q—DETAILS, COMPONENTS, OR ACCESSORIES FOR MACHINE TOOLS, e.g. ARRANGEMENTS FOR COPYING OR CONTROLLING; MACHINE TOOLS IN GENERAL CHARACTERISED BY THE CONSTRUCTION OF PARTICULAR DETAILS OR COMPONENTS; COMBINATIONS OR ASSOCIATIONS OF METAL-WORKING MACHINES, NOT DIRECTED TO A PARTICULAR RESULT
    • B23Q2701/00—Members which are comprised in the general build-up of a form of the machine
    • B23Q2701/01—Frames or slideways for lathes; Frames for boring machines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23Q—DETAILS, COMPONENTS, OR ACCESSORIES FOR MACHINE TOOLS, e.g. ARRANGEMENTS FOR COPYING OR CONTROLLING; MACHINE TOOLS IN GENERAL CHARACTERISED BY THE CONSTRUCTION OF PARTICULAR DETAILS OR COMPONENTS; COMBINATIONS OR ASSOCIATIONS OF METAL-WORKING MACHINES, NOT DIRECTED TO A PARTICULAR RESULT
    • B23Q2703/00—Work clamping
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Definitions

  • This invention relates to an improved process for producing lactams. More particularly, this invention pertains to a process for producing lactams improved in that useful components are recovered from process waste waters simultaneously with conversion of residues into harmless compounds by specific treatment of process waste waters discharged from the step of producing lactams.
  • Lactams are generally produced by submitting cycloalkanone oximes (e.g. cyclohexanone oxime) to Beckmann rearrangement by use of a concentrated sulfuric acid or fuming sulfuric acid, neutralizing the rearranged mixture with ammonia, followed by removal of ammonium sulfate from the neutralized product through stratification, then extracting lactams with a suitable solvent from the remaining layer and purifying the extract by distillation.
  • the process waste waters obtained thereby as extract residues generally contain caprolactam, organic solvents, ammonium sulfate, water-soluble organic impurities containing sulfur, etc.
  • the principal object of the present invention is to provide a process for producing lactams which reduces the drawbacks of the prior art as mentioned above.
  • the present invention provides a process for producing lactams by effecting Beckmann rearrangement of alkanone oximes with a concentrated sulfuric acid or fuming sulfuric acid, neutralizing the rearranged mixture with ammonia and separating ammonium sulfate and lactams from the resulting product, wherein the improvement comprises treating the waste waters after separation of said ammonium sulfate and lactams in accordance with the following steps:
  • the present invention is inclusive of the embodiment wherein organic solvents contained in the distillates obtained from the concentration steps as mentioned above are recovered for reuse and also of the embodiment wherein sulfuric acid is produced by conventional method from the sulfur dioxide formed in the combustion step and recycled to the rearrangement step.
  • the waste waters after separation of ammonium sulfate and lactams as mentioned above are fed to the concentration step 1 through line 7.
  • the distillate from the concentration step 1 is introduced into the condensation step 5 through line 12.
  • Organic solvents recovered by separation after condensation treatment may be provided for use in extraction of lactams.
  • the condensed water withdrawn from line 13 can either be used in other uses or discarded.
  • the sulfur dioxide, if present in the distillate, is discharged from line 15 and may be subjected to combustion treatment by being absorbed in the waste waters to be fed into the combustion step 4 as mentioned below or alternatively be converted to sulfuric acid by being incorporated into the gas discharged after said combustion treatment.
  • the thus concentrated waste liquor from the step 1 is then fed to the other concentration step 2 through line 8 to be further concentrated.
  • the distillate from the step 2 withdrawn through line 16 consists substantially of water and, after being condensed, may either be discarded or utilized as processing water.
  • the waste waters concentrated in the step 2 are fed through line 9 to the extraction step 3, wherein extraction treatment is carried out with the organic solvent supplied through line 20 to separate lactams contained in the waste waters by extraction.
  • the extract mixture is withdrawn through line 17 and introduced into the separation step 6 wherein separation is conducted by conventional methods such as distillation.
  • the lactam separated is recovered through line 18 and the organic solvent separated through line 19 to be recycled for reuse.
  • the residue after extraction of the lactam is introduced through line 10 into the combustion step 4.
  • the sulfur dioxide formed by the oxidative combustion of extraction residue is converted by conventional method via sulfuric anhydride into sulfuric acid or fuming sulfuric acid. The thus formed sulfuric acid can be used in the rearrangement step in the procedure for producing lactams.
  • the concentration of the waste waters should be conducted in two steps. If it is conducted by one step, organic solvents contained in the waste waters can be separated with difficulty. In addition, it is also difficult to utilize effectively the distillates produced, especially steam. On the other hand, concentration treatment by three or more steps is economically disadvantageous in view of installation costs.
  • the concentration treatment in the first step is conducted desirably at a temperature ranging from about 80° to 130° C under a pressure ranging from 400 mm Hg to 2.7 Kg/cm 2 . If the concentration temperature under a pressure within said range is lower than the range as specified above, it is difficult to separate the organic solvents from the waste waters and the distillates obtained are often disadvantageous in utilization as heat source for the second concentration step. On the contrary, if the temperature exceeds said range, lactams contained in the waste waters may undergo polymerization to result in losses or deterioration in quality of the lactams recovered from the subsequent step. Furthermore, unfavorable results in aspect of corrosion of equipment materials are liable to be caused at a too high temperature.
  • the extent of concentration in the first step is required to be in the range from 85 to 75 wt.%; in terms of the water concentration. If the extent of concentration is too low, i.e. over 85 wt.% water concentration, there are disadvantages in thermal efficiency as well as in a difficult separation procedure by stratification when organic solvents are recovered from condensed distillates. On the contrary, if it is too high, i.e. less than 75 wt.% water concentration, the procedure is also disadvantageous in thermal efficiency and the concentration of sulfur dioxide formed by decomposition of ammonium sulfate is so high that unfavorable results are liable to be caused by corrosion of equipment materials.
  • the second concentration step is carried out desirably at a temperature ranging from about 40° to 80° C under a pressure ranging from 50 to 400 mmHg until the water concentration becomes 70 to 15 wt.%. If the temperature is lower than said range under a pressure in the specified range, it is difficult to maintain an appropriate temperature at the time of extraction treatment of lactams in the next step, whereby decrease in extraction efficiency is caused. On the other hand, if the temperature is higher than said range, the extraction operation cannot smoothly be carried out since it is close to the boiling point of the organic solvent to be used in the extraction step as mentioned above. Furthermore, a lower extent of concentration than the range as specified above will cause decrease in recovery of lactams in the next extraction step.
  • the organic solvents to be used in the extraction step may be those known in the art as lactam extraction solvents, typically aromatic hydrocarbon such as benzene, toluene and the like.
  • the amount of the solvents as well as the extraction conditions are not specifically limited but conventional methods can be feasible.
  • the pH of the liquid to be extracted is preferably controlled at about 2.5 to about 6.
  • a small amount of organic solvents contained in the extract residue is preferrably recovered by evaporation before the residue is charged into the combustion step.
  • the combustion is performed desirably at a temperature ranging from about 800° to 1300° C.
  • the combustion is carried out by charging sulfur simultaneously with oxygen or molecular oxygen containing gas. If desired, they may directly be supplied to a sulfur burning furnace for production of sulfur dioxide. If the combustion temperature is lower than 800° C, no complete combustion can be effected, while unfavorable formation of nitrogen oxides is observed when the temperature is higher than 1300° C.
  • the process of the invention can bring about various advantages by treatment of the waste waters discharged out from the lactam manufacturing plants as mentioned above, namely:
  • Cyclohexanone oxime was subjected to Beckmann rearrangement by using fuming sulfuric acid. The rearranged mixture was neutralized with ammonia. After removal of ammonium sulfate by stratification from the neutralized product, followed by separation of caprolactam by benzene extraction, the waste waters obtained was treated in accordance with the flow as shown in the accompanying drawing to obtain the result as shown in the following Table.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Treating Waste Gases (AREA)
  • Other In-Based Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heat Treatment Of Water, Waste Water Or Sewage (AREA)
  • Physical Water Treatments (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Hydrogenated Pyridines (AREA)
US05/698,122 1975-06-24 1976-06-21 Process for producing caprolactam Expired - Lifetime US4072678A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JA50-79198 1975-06-24
JP50079198A JPS523261A (en) 1975-06-24 1975-06-24 Purification method for polluted water

Publications (1)

Publication Number Publication Date
US4072678A true US4072678A (en) 1978-02-07

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Family Applications (1)

Application Number Title Priority Date Filing Date
US05/698,122 Expired - Lifetime US4072678A (en) 1975-06-24 1976-06-21 Process for producing caprolactam

Country Status (7)

Country Link
US (1) US4072678A (de)
JP (1) JPS523261A (de)
DE (1) DE2628085C3 (de)
FR (1) FR2315502A1 (de)
GB (1) GB1508942A (de)
IT (1) IT1062414B (de)
NL (1) NL7606726A (de)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5264571A (en) * 1991-09-30 1993-11-23 Basf Aktiengesellschaft Preparation of caprolactam by Beckmann rearrangement of cyclohexanone oxime
WO2000066561A1 (en) * 1999-04-29 2000-11-09 Dsm N.V. Process for the preparation of caprolactam
US6191274B1 (en) 1996-02-17 2001-02-20 Dsm N.V. Recovery of ε-caprolactam
US20020131924A1 (en) * 2001-03-16 2002-09-19 Jurgen Heuser Process for the reduction of concentration of nitrates and/or nitrogen-containing compounds by means of SO2
US7022844B2 (en) 2002-09-21 2006-04-04 Honeywell International Inc. Amide-based compounds, production, recovery, purification and uses thereof
KR101810704B1 (ko) 2009-12-18 2017-12-19 캡 쓰리 비 브이 막 처리에 의한 카프로락탐 회수방법

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0826665A1 (de) * 1996-09-02 1998-03-04 Dsm N.V. Gewinnung von epsilon-Caprolactam aus wässrigen Gemischen
AU2016271729C1 (en) 2015-05-29 2022-04-07 Kuraray Co., Ltd. Fibrous sheet

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA557462A (en) * 1958-05-13 Schaffler Alfred PROCESS AND PLANT FOR THE RECOVERY OF .epsilon.-CAPROLACTAM
US2973355A (en) * 1961-02-28 Process for the production of pure x-caprolactim
US3264060A (en) * 1966-08-02 Simultaneous recovery of pure ammoni- um sulfate and pure lactams from re- arrangement mixtures of alicyclic ketoximes
US3795731A (en) * 1971-02-19 1974-03-05 Zieren Chemiebau Gmbh Dr A Process for the combustion of ammonium sulfate
US3852272A (en) * 1971-05-07 1974-12-03 Stamicarbon Process for removing lactams
US3852273A (en) * 1971-05-07 1974-12-03 Stamicarbon Process for preparing and recovering lactams
US3954955A (en) * 1971-08-31 1976-05-04 Davy Powergas Gmbh Process for working up the wash solution obtained in the washing of SO2 -containing off-gases
US3992372A (en) * 1974-04-02 1976-11-16 Basf Aktiengesellschaft Processing polycaprolactam extraction liquors
US4036830A (en) * 1975-05-01 1977-07-19 Stamicarbon B.V. Process for the recovery of pure ε-caprolactam from an aqueous solution thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA557462A (en) * 1958-05-13 Schaffler Alfred PROCESS AND PLANT FOR THE RECOVERY OF .epsilon.-CAPROLACTAM
US2973355A (en) * 1961-02-28 Process for the production of pure x-caprolactim
US3264060A (en) * 1966-08-02 Simultaneous recovery of pure ammoni- um sulfate and pure lactams from re- arrangement mixtures of alicyclic ketoximes
US3795731A (en) * 1971-02-19 1974-03-05 Zieren Chemiebau Gmbh Dr A Process for the combustion of ammonium sulfate
US3852272A (en) * 1971-05-07 1974-12-03 Stamicarbon Process for removing lactams
US3852273A (en) * 1971-05-07 1974-12-03 Stamicarbon Process for preparing and recovering lactams
US3954955A (en) * 1971-08-31 1976-05-04 Davy Powergas Gmbh Process for working up the wash solution obtained in the washing of SO2 -containing off-gases
US3992372A (en) * 1974-04-02 1976-11-16 Basf Aktiengesellschaft Processing polycaprolactam extraction liquors
US4036830A (en) * 1975-05-01 1977-07-19 Stamicarbon B.V. Process for the recovery of pure ε-caprolactam from an aqueous solution thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5264571A (en) * 1991-09-30 1993-11-23 Basf Aktiengesellschaft Preparation of caprolactam by Beckmann rearrangement of cyclohexanone oxime
US6191274B1 (en) 1996-02-17 2001-02-20 Dsm N.V. Recovery of ε-caprolactam
WO2000066561A1 (en) * 1999-04-29 2000-11-09 Dsm N.V. Process for the preparation of caprolactam
US20020131924A1 (en) * 2001-03-16 2002-09-19 Jurgen Heuser Process for the reduction of concentration of nitrates and/or nitrogen-containing compounds by means of SO2
US6761828B2 (en) * 2001-03-16 2004-07-13 Bayer Aktiengesellschaft Process for the reduction of concentration of nitrates and/or nitrogen-containing compounds by means of SO2
US7022844B2 (en) 2002-09-21 2006-04-04 Honeywell International Inc. Amide-based compounds, production, recovery, purification and uses thereof
KR101810704B1 (ko) 2009-12-18 2017-12-19 캡 쓰리 비 브이 막 처리에 의한 카프로락탐 회수방법

Also Published As

Publication number Publication date
GB1508942A (en) 1978-04-26
IT1062414B (it) 1984-10-10
FR2315502B1 (de) 1979-04-06
NL7606726A (nl) 1976-12-28
FR2315502A1 (fr) 1977-01-21
JPS523261A (en) 1977-01-11
DE2628085C3 (de) 1980-06-26
DE2628085A1 (de) 1977-01-27
JPS56119B2 (de) 1981-01-06
DE2628085B2 (de) 1979-09-27

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